Storage-stable solutions of accelerator systems

Abstract

Solutions of accelerator systems comprising a binary system comprising a) 10 to 90% by weight of a salt of formula I [Me]mx(+)[R]ny(-)(I), wherein x and y are the respective number of charges and m and n are each a number 1, 2, 3 or 4, Me is a metal atom and R is the radical of an alcohol, phenol or thiophenol or of a carboxylic acid or thiocarboxylic acid, or 10 to 90% by weight of a salt of formula II [Me1]mx(+)[A]ny(-)(II), with an organic complex former containing one or more hetero atoms having free electron pairs, wherein Me1 is a metal atom or a group of the formula N(R1)4, S(R1)3 or P(R1)4 wherein each R1 independently of the others is hydrogen, an unsubstituted or substituted C1-C6alkyl or aryl radical, A is any anion and x, y, m and n are as defined above, and b) 90 to 10% by weight of an organic solvent containing at least one -OH, -OR1, -COOH, -COOR1, -COR1 or -CON(R1)2 group wherein R1 is hydrogen, an unsubstituted or substituted C1-C6alkyl or aryl radical, are storage-stable with respect to temperature and time and do not precipitate, and the use thereof, for example for accelerating the hardening of epoxy resin/amine combinations, the drying times being in the range of about 15 to 40 minutes.

What is claimed is: 
     
       1. A solution of an accelerator system, which comprises a binary system comprising: a) 10 to 90% by weight of a salt of formula I   [Me].sub.m.sup.x⊕ [R].sub.n.sup.y⊖             (I),     wherein x and y are the respective number of charges and m and n are each a number 1, 2, 3 or 4, Me is a metal atom and R is the radical of an alcohol, phenol or thiophenol or of a carboxylic acid or thiocarboxylic acid, or   10 to 90% by weight of a salt of formula II   [Me.sub.1 ].sub.m.sup.x⊕ [A].sub.n.sup.y⊖      (II),       with an organic complex former containing one or more hetero atoms having free electron pairs,   wherein Me 1  is a metal atom or a group of the formula N(R 1 ) 4 , S(R 1 ) 3  or P(R 1 ) 4  wherein each R 1  independently of the others is hydrogen, an unsubstituted or substituted C 1  -C 6  alkyl or aryl radical, A is any anion and x, y, m and n are as defined above, and wherein the salts of formula II used contain no water of crystallisation and also contain solvents that are anhydrous, and     b) 90 to 10% by weight of an organic solvent selected from a monohydric alcohol and a solvent containing at least one --OR 1  or --COR 1  group wherein R 1  is hydrogen, an unsubstituted or substituted C 1  -C 6  alkyl or aryl radical.   
     
     
       2. A solution of an accelerator system according to claim 1, wherein the accelerator system comprises 25 to 75% by weight of a salt of formula I or a salt of formula II with the complex former, and 25 to 75% by weight of a solvent b) according to claim 1. 
     
     
       3. A solution of an accelerator system according to claim 1, wherein in formula I Me is Li, Na, K, Mg, Ca, Ba, Fe, Co, Ni, Cu, Zn, Sn, Al, La or Ce and R is the radical of a phenol or thiophenol of formula III ##STR7## wherein X is O-- or S--, n is a number 1 or 2, and   Y is a group of formula ##STR8## wherein o is a number 0, 1, 2, 3 or 4, each R 2  is hydrogen or independently of the other unsubstituted or substituted C 1  -C 20  alkyl, and m is a number 1, 2 or 3, and the solvent is a solvent according to claim 1.   
     
     
       4. A solution of an accelerator system according to claim 3, wherein in formula I Me is Li, Ba, Ca, Zn, Al, Fe or La and R is 2,4,6-tris(dimethylaminomethyl)phenol and the solvent is methanol, ethanol, a propanol, a butanol, methyl ethyl ketone, methyl isobutyl ketone, dimethoxyethane or methoxypropyl alcohol. 
     
     
       5. A solution of an accelerator system according to claim 1, wherein in formula II Me 1  is Li, Na, K, Mg, Ca, Ba, Fe, Co, Ni, Cu, Zn, Sn, Al, La, Ce or N(R 1 ) 4 , S(R 1 ) 3  and P(R 1 ) 4 , with R 1  being as defined in claim 1, and A is Cl, Br, I, NO 3 , NO 2 , ClO 3 , ClO 4 , SbF 6 , AsF 6 , PF 6 , BF 4 , CN, SCN, R 3  --COO, R 3  --SO 3 , R 3  --SO 2 , PO 4 , HPO 4  or H 2  PO 4  wherein R 3  is unsubstituted or substituted C 1  -C 6  alkyl or aryl, and the organic complex former either corresponds to formula IV ##STR9## wherein R 4  is hydrogen, C 1  -C 20  alkyl or trialkyl(C 1  -C 4 )silyl, u is a number 0, 1 or 2, R 5  is C 1  -C 6  alkyl and v is a number 1, 2 or 3, or is a malic acid di(C 1  -C 4 )alkyl ester, an N,N-di(C 1  -C 4 )alkylphenylalanine (C 1  -C 4 )alkyl ester, thiourea or unsubstituted or substituted salicylic acid or a piperidine derivative, and the solvent is a solvent according to claim 1.   
     
     
       6. A solution of an accelerator system according to claim 5, wherein Me 1  is Li, Ca, Fe or La and A is NO 3 , Br, I, triflate, capronate, perchlorate or propionate and the organic complex former is benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenylbutyl ether, 2,4,6-tris(dimethylaminomethyl)phenyloctyl ether, 3-dimethylaminophenol, 3-dimethylaminophenylbutyl ether, 3-dimethylaminophenyloctyl ether, malic acid dimethyl ester, N,N-dimethylphenylalanine methyl ester, piperidinoethylamine, N,N-dimethylaminoethylpiperidine, 2,4,6-tris(dimethylaminomethyl)phenol, thiourea, salicylic acid or 2,4,6-tris(dimethylaminomethyl)phenyl-trimethylsilyl ether, and the solvent is methanol, ethanol, a propanol, a butanol, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol or methoxypropyl alcohol. 
     
     
       7. A solution of an accelerator system according to claim 1, wherein the accelerator system comprises 10 to 90% by weight of a stoichiometric 1:2 complex comprising a salt of formula II   [Me.sub.1 ].sub.m.sup.⊕ [A].sub.n.sup.y⊖       (II),     wherein the symbols are as defined in claim 1, with an organic complex former containing one or more hetero atoms having free electron pairs, and   90 to 10% by weight of an organic solvent containing at least one --OH, --OR 1 , --COOH, --COOR 1 , --COR 1  or --CON(R 1 ) 2  group wherein R 1  is hydrogen, an unsubstituted or substituted C 1  -C 6  alkyl or aryl radical.   
     
     
       8. The preparation of a solution of an accelerator system according to claim 1 by mixing the individual components at a temperature of from 10° C. to 40° C. 
     
     
       9. A method of hardening epoxy resin/amine combinations by adding to these combinations a solution of an accelerator according to claim 1.